Nonclassical Mechanism of Metal-Enhanced Photoluminescence of Quantum Dots.

Metal-enhanced photoluminescence is able to provide a robust signal even from a single emitter and is promising in applications in biosensors and optoelectronic devices. However, its realization with semiconductor nanocrystals (e.g., quantum dots, QDs) is not always straightforward due to the hidden and not fully described interactions between plasmonic nanoparticles and an emitter. Here, we demonstrate nonclassical enhancement (i.e., not a conventional electromagnetic mechanism) of the QD photoluminescence at nonplasmonic conditions and correlate it with the charge exchange processes in the system, particularly with high efficiency of the hot-hole generation in gold nanoparticles and the possibility of their transfer to QDs. The hole injection returns a QD from a charged nonemitting state caused by hole trapping by surface and/or interfacial traps into an uncharged emitting state, which leads to an increased photoluminescence intensity. These results open new insights into metal-enhanced photoluminescence, showing the importance of the QD surface states in this process.

Engineering of the Photon Local Density of States: Strong Inhibition of Spontaneous Emission near the Resonant and High-Refractive Index Dielectric Nano-objects.

Metallic or dielectric nano-objects change the photon local density of states of closely placed emitters, particularly when plasmon or Mie resonances are present. Depending on the shape and material of these nano-objects, they may induce either a decrease or an increase in decay rates of the excited states of the emitter. In this work, we consider the reduction of the probability of optical transitions in emitters near high-refractive index dielectric (silicon and zinc selenide) nanoparticles. We tune the spectral positions of magnetic and electric modes of nanocylinders to obtain the largest overlap of the valleys in the total decay rate spectra for differently oriented dipoles and, in this way, find the highest inhibition of about 80% for randomly oriented emitters. The spectral positions of these valleys are easy to control since the wavelengths of the modes depend on the height and diameter of nanocylinders. The inhibition value is robust to the distance between the emitter and the nanoparticle in the range of nearly 50 nm, which is crucially important for the applications, such as selective optical transition engineering and photovoltaics.

Possible nanoantenna control of chlorophyll dynamics for bioinspired photovoltaics.

In the context of using portions of a photosynthetic apparatus of green plants and photosynthesizing bacteria in bioinspired photovoltaic systems, we consider possible control of the chlorophyll excited state decay rate using nanoantennas in the form of a single metal and semiconductor nanoparticle. Since chlorophyll luminescence competes with electron delivery for chemical reactions chain and also to an external circuit, we examine possible excited state decay inhibition contrary to radiative rate enhancement. Both metal and semiconductor nanoparticles enable inhibition of radiative decay rate by one order of the magnitude as compared to that in vacuum, whereas a metal nanosphere cannot perform the overall decay inhibition since slowing down of radiative decay occurs only along with the similar growth of its nonradiative counterpart whereas a semiconductor nanoantenna is lossless. Additionally, at normal orientation of the emitter dipole moment to a nanoparticle surface, a silicon nanoparticle promotes enhancement of radiative decay by one order of the magnitude within the whole visible range. Our results can be used for other photochemical or photovoltaic processes, and strong radiative decay enhancement found for dielectric nanoantennas paves the way to radiative decays and light emitters engineering without non-radiative losses.

Electroabsorption by 0D, 1D, and 2D nanocrystals: a comparative study of CdSe colloidal quantum dots, nanorods, and nanoplatelets.

This work presents a comprehensive study of electroabsorption in CdSe colloidal quantum dots, nanorods, and nanoplatelets. We experimentally demonstrate that the exposure of the nanoplatelets to a dc electric field leads to strong broadening of their lowest-energy heavy-hole absorption band and drastically reduces the absorption efficiency within the band. These are results of the quantum-confined Stark and Franz­Keldysh effects. The field-induced change in the nanoplatelets' absorption is found to be more than 10 times the change in the absorption by the quantum dots. We also demonstrate that the electroabsorption by the nanorods is weaker than that by the quantum dots and nanoplatelets and reveal an unusual dependence of the differential absorption changes on the nanoplatelet thickness: the thicker the nanoplatelet, the smaller the change.

Vibrational spectroscopy of N'-(Adamantan-2-ylidene)thiophene-2-carbohydrazide, a potential antibacterial agent.

Vibrational states of the newly synthesized molecule N'-(Adamantan-2-ylidene)thiophene-2-carbohydrazide, a potential antibacterial agent, are examined experimentally for the crystalline phase and analyzed based on quantum chemical modelling of the solitary molecule and of the dimer, and assignment of the observed vibrational frequencies is proposed. Modelling of the title molecule dimer is found to describe better the experimentally observed vibration frequencies for the crystalline phase than calculations performed for a solitary molecule. Contributions from adamantane and thiophene parts within the molecule are identified. Additionally, multiple hydrogen bonds have been revealed both experimentally and computationally, inherent in the crystalline phase contrary to a solitary molecule. The spectroscopic findings correlate with the calculated interatomic distances which were found to change in the dimer versus a single molecule and to correspond better to the X-ray analysis data of the title compound in the crystalline phase.

Nonresonant surface-enhanced Raman scattering of ZnO quantum dots with Au and Ag nanoparticles.

Pronounced 10(4)-fold enhancement of Raman scattering has been obtained for ZnO nanocrystals on substrates coated with 50 nm Ag nanoparticles under nonresonant excitation with a commercial red-emitting laser. This makes feasible beyond 10(-18) mole detection of ZnO nanocrystals with a commercial setup using a 0.1 mW continuous wave laser and can be purposefully used in analytical applications where conjugated nanocrystals serve as Raman markers. For Au-coated surfaces the enhancement is much lower and the heating effects in the course of Raman experiments are pronounced.

Anisotropic emission from multilayered plasmon resonator nanocomposites of isotropic semiconductor quantum dots.

We propose and demonstrate a nanocomposite localized surface plasmon resonator embedded into an artificial three-dimensional construction. Colloidal semiconductor quantum dots are assembled between layers of metal nanoparticles to create a highly strong plasmon-exciton interaction in the plasmonic cavity. In such a multilayered plasmonic resonator architecture of isotropic CdTe quantum dots, we observed polarized light emission of 80% in the vertical polarization with an enhancement factor of 4.4, resulting in a steady-state anisotropy value of 0.26 and reaching the highest quantum efficiency level of 30% ever reported for such CdTe quantum dot solids. Our electromagnetic simulation results are in good agreement with the experimental characterization data showing a significant emission enhancement in the vertical polarization, for which their fluorescence decay lifetimes are substantially shortened by consecutive replication of our unit cell architecture design. Such strongly plasmon-exciton coupling nanocomposites hold great promise for future exploitation and development of quantum dot plasmonic biophotonics and quantum dot plasmonic optoelectronics.